Process for the preparation of fluoroolefin compounds

ABSTRACT

The subject of the invention is a process for the preparation of fluoroolefin compounds. It relates more particularly to a process for manufacturing a (hydro)fluoroolefin compound comprising (i) bringing at least one compound comprising from three to six carbon atoms, at least two fluorine atoms and at least one hydrogen atom, provided that at least one hydrogen atom and one fluorine atom are located on adjacent carbon atoms, into contact with potassium hydroxide in a stirred reactor, containing an aqueous reaction medium, equipped with at least one inlet for the reactants and with at least one outlet, in order to give the (hydro)fluoroolefin compound, which is separated from the reaction medium in gaseous form, and potassium fluoride, (ii) bringing the potassium fluoride formed in (i) into contact, in an aqueous medium, with calcium hydroxide in order to give potassium hydroxide and to precipitate calcium fluoride, (iii) separation of the calcium fluoride precipitated in step (ii) from the reaction medium and (iv) optionally, the reaction medium is recycled after optional adjustment of the potassium hydroxide concentration to step (i).

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a Continuation Application of U.S. application Ser. No. 14/695,210, filed Apr. 24, 2015; which is a Continuation Application of U.S. application Ser. No. 13/144,239, filed Oct. 3, 2011, issued Apr. 28, 2015 as U.S. Pat. No. 9,018,429; which is a National Phase Application of International Application No. PCT/FR2010/050043, filed Jan. 12, 2010, which claims priority under 35 U.S.C. §119 to French Patent Application No. FR0950157, filed Jan. 13, 2009.

FIELD OF THE INVENTION

The subject of the invention is a process for the preparation of fluoroolefin compounds. The invention relates more particularly to a process for the preparation of hydrofluoropropenes.

TECHNOLOGICAL BACKGROUND

Hydrofluorocarbons (HFCs) and in particular hydrofluoroollefins (HFOs), such as 2,3,3,3-tetrafluoro-1-propene (HFO-1234yf), are compounds known for their properties of refrigerants and heat-exchange fluids, extinguishers, propellants, foaming agents, blowing agents, gaseous dielectrics, polymerization medium or monomer, support fluids, agents for abrasives, drying agents and fluids for energy production units. Unlike CFCs and HCFCs, which are potentially dangerous to the ozone layer, HFOs do not comprise chlorine and thus do not present a problem for the ozone layer.

1,2,3,3,3-Pentafluoropropene (HFO-1225ye) is a synthetic intermediate in the manufacture of 2,3,3,3-tetrafluoro-1-propene (HFO-1234yf).

The majority of the processes for the manufacture of hydrofluoroolefins involve a dehydrohalogenation reaction. Thus, the document WO 03/027051 describes a process for the manufacture of fluoroolefins of formula CF₃CY═CX_(n)H_(p), in which X and Y each represent a hydrogen atom or a halogen atom chosen from fluorine, chlorine, bromine or iodine and n and p are integers and can independently take the value zero, 1 or 2, provided that (n+p)=2, which comprises bringing a compound of formula CF₃C(R¹ _(a)R² _(b))C(R³ _(c)R⁴ _(d)), with R¹, R², R³ and R⁴ independently representing a hydrogen atom or a halogen atom chosen from fluorine, chlorine, bromine or iodine, provided that at least one of R¹, R², R³ and R⁴ is a halogen atom and that at least one hydrogen atom and one halogen atom are situated on adjacent carbon atoms, a and b being able independently to take the value zero, 1 or 2, provided that (a+b)=2, and c and d being able independently to take the value zero, 1, 2 or 3, provided that (c+d)=3, into contact with at least one alkali metal hydroxide in the presence of a phase transfer catalyst.

This document teaches, in Example 2, that, in the absence of a phase transfer catalyst, there is no reaction when 1,1,1,3,3-pentafluoropropane (HFC-245fa) is brought into contact with a 50% by weight aqueous potassium hydroxide (KOH) solution at ambient temperature and under pressure for 24 hours.

In addition, this document teaches a reaction temperature of between −20° C. and 80° C.

The document WO 2008/075017 illustrates the dehydrofluorination reaction of 1,1,1,23-hexafluoropropane (HFC-236ea) to give 1,2,3,3,3-pentafluoropropene (HFO-1225ye) at 150° C. in the presence of a 50% by weight aqueous KOH solution. In the absence of a phase transfer catalyst, the conversion after 3 and a half hours is 57.8% and the selectivity for HFO-1225ye is 52.4% (Test 1). In the presence of a phase transfer catalyst, this conversion is reached after only 2.5 hours and the selectivity is virtually unchanged (Test 4). As indicated in Table 2 of this document, it is necessary to use an organic solvent in order to increase the selectivity for HFO-1225ye.

WO 2007/056194 describes the preparation of HFO-1234yf by dehydrofluorination of 1,1,1,2,3-pentafluoropropane (HFC-245eb) either with an aqueous KOH solution or in the gas phase in the presence of a catalyst, in particular over a catalyst based on nickel, carbon or a combination of these.

The document Knunyants et al., Journal of the USSR Academy of Sciences, Chemistry Department, “Fluoroolefin Reactions”, Report 13, “Catalytic Hydrogenation of Perfluoroolefins”, 1960, clearly describes various chemical reactions on fluorinated compounds. This document describes the dehydrofluorination of 1,1,1,2,3,3-hexafluoropropane (236ea) by passing through a suspension of KOH powder in dibutyl ether, to produce 1,2,3,3,3-pentafluoro-1-propene (HFO-1225ye) with a yield of only 60%. This document also describes the dehydrofluorination of 1,1,1,2,3-pentafluoropropane (HFC-245eb) to give 2,3,3,3-tetrafluoro-1-propene (HFO-1234yf) by passing into a suspension of KOH powder in dibutyl ether with a yield of only 70%.

Furthermore, FIG. 2 on page 51 of Part 2 of the nouveau traité de chimie minérale [New Treatise on Inorganic Chemistry] by P. Pascal, Ed, 1963, shows the appearance of the liquid/solid equilibria of the water and potassium hydroxide system and the measurements are collated in the Table on page 52.

The dehydrofluorination reactions such as described above result, besides the desired hydrofluoroolefin compound, in the formation of water and potassium fluoride. Furthermore, the implementation of such a reaction in continuous mode is not easy on an industrial scale since at least three phases (gas, liquid and solid) are involved.

The present invention provides a process for the continuous and semi-continuous manufacture of a (hydro)fluoroolefin compound that makes it possible to overcome the aforementioned drawbacks.

The subject of the present invention is therefore a process for the continuous or semi-continuous manufacture of a (hydro)fluoroolefin compound comprising (i) bringing at least one compound comprising from three to six carbon atoms, at least two fluorine atoms and at least one hydrogen atom, provided that at least one hydrogen atom and one fluorine atom are located on adjacent carbon atoms, into contact with potassium hydroxide in a stirred reactor, containing an aqueous reaction medium, equipped with at least one inlet for the reactants and with at least one outlet, in order to give the (hydro)fluoroolefin compound, which is separated from the reaction medium in gaseous form, and potassium fluoride, (ii) bringing the potassium fluoride formed in (i) into contact, in an aqueous medium, with calcium hydroxide in order to give potassium hydroxide and to precipitate calcium fluoride, (iii) separation of the calcium fluoride precipitated in step (ii) from the reaction medium and (iv) optionally, the reaction medium is recycled after optional adjustment of the potassium hydroxide concentration to step (i).

The present invention thus makes it possible to obtain an advantageous process since, on the one hand, potassium hydroxide is more reactive than calcium hydroxide in the dehydrofluorination reaction and, on the other hand, calcium fluoride is a reusable by-product. The process according to the present invention preferably provides a (hydro)fluoroolefin compound comprising three carbon atoms, advantageously a (hydro)fluoroolefin compound represented by the formula (I):

CF₃CY═CX_(n)H_(p)   (I)

in which Y represents a hydrogen atom or a halogen atom chosen from fluorine, chlorine, bromine or iodine and X represents a halogen atom chosen from fluorine, chlorine, bromine or iodine; n and p are integers and may independently take the value zero, 1 or 2 provided that (n+p)=2, by bringing a compound of formula CF₃CYRCR′X_(n)H_(p), in which X, Y, n and p have the same meaning as in formula (I) and R represents a fluorine atom when R′ represents a hydrogen atom or R represents a hydrogen atom when R′ represents a fluorine atom into contact with potassium hydroxide.

The present invention is very particularly suitable for the manufacture of a compound of formula (Ia):

CF₃—CF═CHZ   (Ia)

in which Z represents a hydrogen or fluorine atom, from a compound of formula CF₃CFRCHR′Z, in which Z has the same meaning as in formula (Ia) and R represents a fluorine atom when R⁴⁰ represents a hydrogen atom or R represents a hydrogen atom when R⁴⁰ represents a fluorine atom.

Thus, 2,3,3,3-tetrafluoropropene may be obtained by dehydrofluorination of 1,2,3,3,3-pentafluoropropane with KOH and/or 1,2,3,3,3-pentafluoropropene by dehydrofluorination of 1,1,1,2,3,3-hexafluoropropane with KOH. The 1,2,3,3,3-pentafluoropropene may be in the cis and/or trans isomer form.

The present invention may also be used for the manufacture of 1,3,3,3-tetrafluoropropene by dehydrofluorination of 1,1,3,3,3-pentafluoropropane with KOH.

In the remainder of the text, the limits of the concentration and temperature ranges given are included in said ranges.

In step (i) of the process according to the present invention, the potassium hydroxide may represent between 10 and 90% by weight relative to the weight of the water and KOH mixture present in the aqueous reaction medium, preferably between 20 and 86% and advantageously between 55 and 75% by weight. Depending on the content, the potassium hydroxide may be in the form of an aqueous solution or in the molten state. This high KOH content leads to an increase in the conversion rate of the hydrofluoroalkane to hydrofluoroalkene. Moreover, due to this concentrated KOH medium, the HF formed in (i) reacts immediately with KOH to form KF that is less corrosive than HF, which makes it possible to use, downstream of the dehydrofluorination reactor, carbon steel reactors that are of low cost compared to reactors made of an inert material (UB6 or Inconel) for the dehydrofluorination reactor. Moreover, the “trapping” of HT in the form of KF facilitates the separation of the various products from one another (HF having a tendency to form azeotropes with hydrofluoroalkanes and hydrofluoroalkenes), thus, a simple distillation is sufficient to separate the products from one another.

The step (i) is generally carried out at a temperature such that the water formed during the dehydrofluorination reaction is removed, partly or completely, from the reaction medium via entrainment of the gas stream comprising the (hydro)fluoroolefin compound from the stirred reactor. This temperature is preferably between 80 and 180° C., advantageously between 125 and 180° C., and very particularly between 145 and 165° C. The evaporation of the water during step (i) is in the direction of increasing the conversion rate of the hydrofluoroalkane to hydrofluoroalkene.

The dehydrofluorination reaction of step (i) may be carried out at atmospheric pressure, but it is preferred to work at a pressure above atmospheric pressure. Advantageously, this pressure is between 1.1 and 2.5 bar.

The reaction of step (ii) may be carried out in a stirred reactor or fluidized bed reactor by reacting calcium hydroxide, preferably in a suspension in water, with the potassium fluoride from step (i). The reaction temperature may vary to a large extent but for economic reasons, it is preferably between 50 and 150° C.., for example from 75° C. to 120° C. and advantageously between 90 and 120° C.

When a suspension of calcium hydroxide is used in step (ii), the calcium hydroxide represents between 2 and 40% by weight relative to the weight of the suspension.

Advantageously, step (ii) is carried out in the reaction medium from step (i) comprising water, potassium hydroxide and potassium chloride. The potassium fluoride originating from step (i) and supplying step (ii) may be dissolved or in suspension.

The potassium hydroxide represents, in the reaction medium of step (ii), preferably between 2 and 50% by weight relative to the weight of the water and potassium hydroxide mixture of the medium.

When the steps (i) and (ii) are carried out in separate reactors, it is possible to provide a dilution step of the reaction medium between step (i) and step (ii).

The calcium fluoride precipitated in step (ii) is separated from the reaction medium, for example by filtration and/or settling. Prior to the filtration, it is possible to provide a settling step, The calcium fluoride thus separated is then washed with water.

During the settling step, it is possible to make provision for the recycling of a portion of the suspension that is concentrated in calcium fluoride to step (ii). Advantageously, the content of calcium fluoride solids present in the reaction medium of step (ii) is between 5 and 40% by weight.

After separation of the calcium fluoride, the reaction medium with or without the calcium fluoride washing waters may be recycled to step (i) after optional adjustment of the potassium hydroxide content.

According to one embodiment of the invention, steps (i) and (ii) may be carried out in the same reactor.

It may be advantageous to use an inert gas, preferably nitrogen or hydrogen in the dehydrofluorination step.

The process according to the present invention has the advantage of resulting in high yields even in the absence of a phase transfer catalyst and/or an organic solvent.

The present invention also comprises the combinations of the preferred forms regardless of the embodiment.

EXPERIMENTAL SECTION Example 1

FIG. 1 gives the diagram for one embodiment of the present invention. A stirred reactor (1), made of nickel, equipped with a device for heating and measuring the temperature of the reaction medium, containing a mixture of water and of KOH, is continuously fed with a solution of molten KOH (2) in which the KOH is present at 60% by weight in the water, and with 1,1,1,2,3,3-hexafluoropropane (3). The temperature is kept at 160° C. and the pressure in the reactor is 1.2 bar absolute. The gaseous products exit the reactor via an orifice (4) located in the cover of the reactor and the water contained in the gas stream is removed by condensation (13). The outlet (5) of the reactor (1) is connected to the inlet of the stirred reactor (6) and therefore provides the reactor (6) with the supply of potassium hydroxide, which may be in suspension in the aqueous medium. A 10% by weight suspension of calcium hydroxide in water is introduced into the reactor (6) via the line (7). The reactor (6) is kept at a temperature between 100 and 120° C.

The outlet of the reactor (6) is connected to a filter (8) in order to separate the calcium fluoride from the reaction medium, then wash it with water introduced via the line (9); the aqueous medium separated from the calcium fluoride and also the calcium fluoride washing waters are then recycled to the reactor (1) after adjustment of the KOH concentration; the calcium fluoride is recovered via the line (12). The mixture of molten KOH supplying the reactor (1) is prepared by heating (11) an aqueous solution of 50% by weight of KOH introduced by the line (14) for the purposes of evaporation (removal of water (15)).

Example 2

The procedure of example 1 is followed except that the reactor (1) is continuously supplied with 1,2,3,3,3-pentafluoropropane instead of 1,1,1,2,3,3-hexafluoropropane.

By using a KOH content higher than that from the prior art, improved conversion rates of the hydrofluoroalkane to hydrofluoroalkene (therefore a better productivity), a reusable produce, CaF₂, and lower manufacturing costs of the hydrofluoroalkene are obtained. 

1-11. (canceled)
 12. A process for the manufacture of a fluoroolefin comprising: (a) dehydrofluorinating a fluoroalkane in the presence of KOH to produce a fluoroalkene; (b) withdrawing a reaction stream comprising spent KOH; and (c) recovering spent KOH.
 13. The process of claim 12 wherein the fluoroalkane is comprised of a compound of formula CF₃CYRCR′X_(n)H_(p), in which Y represents a hydrogen atom or a halogen atom chosen from fluorine, chlorine, bromine or iodine and X represents a halogen atom chosen from fluorine, chlorine, bromine or iodine; n and p are integers and may independently take the value zero, 1 or 2 provided that (n+p)=2, and R represents a fluorine atom when R′ represents a hydrogen atom or R represents a hydrogen atom when R′ represents a fluorine atom.
 14. The process of claim 13 wherein the fluoroalkane is 1,1,1,2,3,3-hexafluoropropane (HFC-236ea) or 1,1,1,2,3-pentafluoropropane (HFC-245eb).
 15. The process of claim 12 wherein the fluoroalkene is comprised of a compound of formula CF₃CY═CX_(n)H_(p) in which Y represents a hydrogen atom or a halogen atom chosen from fluorine, chlorine, bromine or iodine and X represents a halogen atom chosen from fluorine, chlorine, bromine or iodine; n and p are integers and may independently take the value zero, 1 or 2 provided that (n+p)=2.
 16. The process of claim 15 wherein the fluoroalkene is 2,3,3,3-tetrafluoropropene (HFO-1234yf) or 1,2,3,3,3-pentafluoropropene (HFO-1225ye).
 17. The process of claim 12 wherein the dehydrofluorination occurs using a continuously stirred tank reactor.
 18. The process of claim 12 wherein the spent KOH is withdrawn from the reactor continuously or intermittently.
 19. The process of claim 12 wherein the spent KOH is purified using at least one separation method.
 20. The process of claim 19 wherein the separation method is phase separation.
 21. The process of claim 12 further comprising, optionally, concentrating the purified KOH and recycling it back to the dehydrofluorination reaction.
 22. The process of claim 12 wherein the reaction stream further comprises KF.
 23. The process of claim 22 further comprising converting KF to KOH in the presence of Ca(OH)₂.
 24. The process of claim 23 further comprising, optionally, concentrating the converted KOH and recycling it back to the dehydrofluorination reaction.
 25. A process for the manufacture of a fluoroolefin comprising: (a) dehydrohalogenating 1,1,1,2,3,3-hexafluoropropane (HFC-236ea) or 1,1,1,2,3-pentafluoropropane (HFC-245eb) in the presence of KOH to produce 2,3,3,3-tetrafluoropropene (HFO-1234yf) or 1,2,3,3,3-pentafluoropropene (HFO-1225ye); (b) withdrawing a reaction stream comprising spent KOH; and (c) recovering spent KOH.
 26. The process of claim 25 wherein the dehydrohalogenation occurs using a continuously stirred tank reactor.
 27. The process of claim 25 wherein the spent KOH is withdrawn from the reactor continuously or intermittently.
 28. The process of claim 25 wherein the spent KOH is purified using at least one separation method.
 29. The process of claim 28, wherein the separation method is phase separation.
 30. The process of claim 25 further comprising, optionally, concentrating the purified KOH and recycling it back to the dehydrohalogenation reaction.
 31. The process of claim 25 wherein the reaction stream further comprises KF.
 32. The process of claim 31 further comprising purifying KF from the reaction stream.
 33. The process of claim 25 further comprising converting KF to KOH in the presence of Ca(OH)₂, optionally, concentrating the KOH and recycling it back to the dehydrohalogenation reaction.
 34. A process for the manufacture of a fluoroolefin comprising: (a) dehydrohalogenating a haloalkane in the presence of KOH to produce a haloalkene; (b) withdrawing a reaction stream comprising spent KOH; and (c) recovering spent KOH. 